Bis chlorotriazine reactive dyes containing a benzylamine linking group

ABSTRACT

Water-soluble reactive dyes of the formula: (1) which are suitable for the coloration of textile materials to give dyeings with good wash-off properties ##STR1## wherein D represents the radical of a water-soluble chromophoric compound; each of R, R 1  and R 2 , independently, represents hydrogen or an optionally substituted alkyl radical and Q represents a radical of the formula: ##STR2## wherein each of X and Y, independently, represents halogen, alkyl, alkoxy, acylamino, nitro, carboxy or sulpho and each of n and m, independently, represents an integer from 0 to 2.

This invention relates to reactive dyes, to their preparation and totheir application to textile substrates.

According to the invention, there are provided water-soluble reactivedyes of the formula: ##STR3## wherein D represents the radical of awater-soluble chromophoric compound; each of R, R¹ and R²,independently, represents hydrogen or an optionally substituted alkylradical and Q represents a radical of the formula: ##STR4## wherein eachof X and Y, independently, represents halogen, nitro, carboxy or sulphoand each of n and m, independently, represents an integer from 0 to 2.

The radical represented by D may be for example a radical of the azo,for example monoazo, disazo and metallised azo, anthraquinone,phthalocyanine, formazan or triphenodioxazine series, carrying one ormore water-solubilising groups, for example sulphonic acid groups.

It is preferred that D is a sulphonated monoazo radical, for example asulphonated azobenzene, azonaphthalene or phenylazonaphthalene radicalin which the aromatic rings may carry, in addition to sulphonic acidgroups, substituents appropriate to water-soluble reactive dyes.

As examples of valuable sulphonated monoazo radicals which may berepresented by D, there may be mentioned radicals of the formula:##STR5## wherein one of U and V is SO₃ H and the other is H, and##STR6## A being a radical of the benzene or naphthalene series.

Particularly useful dyes contain sulphonated monoazo radicals of Formula3 or Formula 4 wherein A is a sulphonated phenyl or naphthyl radical,especially a radical containing a sulpho group in an ortho positionrelative to the azo link. Thus, valuable structures represented by Ainclude: ##STR7## wherein Z¹ represents H, SO₃ H, C₁₋₄ -alkyl(especially methyl) or C₁₋₄ -alkoxy (especially methoxy), and ##STR8##wherein Z² represents H or SO₃ H.

As examples of other valuable sulphonated monoazo radicals which may berepresented by D, there may be mentioned radicals of the formula:##STR9## wherein A is a sulphonated phenyl or naphthyl radical as above,M¹ represents hydrogen, C₁₋₄ -alkyl or C₁₋₄ -alkoxy and M² representshydrogen, C₁₋₄ -alkyl, C₁₋₄ -alkoxy or --NHCOT wherein T denotes C₁₋₄-alkyl or --NH₂.

Particularly useful radical within the scope of Formula 7 include:##STR10## especially those in which A is a sulphonated naphthyl radical,M¹ is hydrogen or C₁₋₄ -alkoxy, for example methoxy, and T is preferablymethyl or amino.

Optionally substituted alkyl radicals which may be represented by R, R¹and R² include C₁₋₈ -, preferably C₁₋₄ -, alkyl radicals which may carrysubstituents selected from halogen, hydroxy, cyano, carboxy, carbamoyl.

The dyes of the invention may be prepared by reacting one mole of an o-,m- or p-aminobenzylamine of the formula: ##STR11## wherein R¹, R², X, Y,n and m are as defined above with two moles of a triazine compound ofthe formula: ##STR12## wherein D and R are as defined above.

The above process can conveniently be carried out by stirring thereactants in an aqueous medium, optionally in the presence of awater-soluble organic solvent, at a temperature of from 20°to 60° C.,and preferably maintaining the pH at from 5 to 9 by adding anacid-binding agent to neutralise the hydrogen halide formed during thereaction. Suitable acid-binding agents are alkali metal hydroxides,carbonates and bicarbonates.

As examples of diamines of Formula 9 there may be mentioned the threeisomeric aminobenzylamines and derivatives in which one or both nitrogenatoms carry C₁₋₄ -alkyl radicals.

Compounds of Formula 10 may be obtained, for example, by reactingcyanuric chloride at 0°-20° C. in aqueous medium, with water solubledyestuff compounds of the formulae DNRH wherein D and R are as definedabove. Such dyestuff compounds have been fully described in the priorart and especially include monoazo dyes obtained from diazo componentssuch as

aniline-2-sulphonic acid,

2-naphthylamine-1,5-disulphonic acid. aniline,

aniline-3-sulphonic acid,

aniline-4-sulphonic acid,

aniline-2,4-disulphonic acid,

aniline-2,5-disulphonic acid,

aniline-3,5-disulphonic acid,

2-methyl-4-sulphoaniline,

2-methyl-5-sulphoaniline,

2-sulpho-4-methylaniline,

2-sulpho-5-methylaniline,

2-methoxy-5-sulphoaniline,

2-sulpho-4-methoxylaniline,

2-chloro-4-sulphoaniline,

2,5-dichloro-4-sulphoaniline,

2-chloro-5-sulphoaniline,

2-sulpho-4-nitroaniline,

2-sulpho-5-nitroaniline,

2-carboxy-5-sulphoaniline,

2-aminonaphthalene-1-sulphonic acid,

2-aminonaphthalene-1,5,7-trisulphonic acid,

2-aminonaphthalene-3,6,8-trisulphonic acid,

2-aminonaphthalene-4,8-disulphonic acid,

2-aminonaphthalene-5,7-disulphonic acid,

2-aminonaphthalene-6-sulphonic acid,

1-aminonaphthalene-4-sulphonic acid,

1-aminonaphthalene-5-sulphonic acid,

1-aminonaphthalene-6-sulphonic acid,

1-aminonaphthalene-7-sulphonic acid,

1-aminonaphthalene-4,8-disulphonic acid,

1-aminonaphthalene-3,8-disulphonic acid,

1-aminonaphthalene-2,5,7-trisulphonic acid, and

1-aminonaphthalene-3,5,7-trisulphonic acid.

The above-mentioned diazo components may be combined with couplingcomponents containing amino groups, the resulting dyes then beingreacted with cyanuric chloride, reaction taking place at the said aminogroups.

Suitable amino group containing coupling components include

aniline,

o-toluidine,

m-toluidine,

o-anisidine,

m-anisidine,

2,6-xylidine,

cresidine,

2,6-dimethoxyaniline,

m-aminoacetanilide,

m-ureidoaniline,

3-amino-4-methoxyacetanilide,

1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid,

1-hydroxy-8-aminonaphthalene-3,5-disulphonic acid,

1-hydroxy-6-aminonaphthalene-3-sulphonic acid,

1-hydroxy-6-methylaminonaphthalene-3-sulphonic acid,

1-hydroxy-7-aminonaphthalene-3-sulphonic acid,

1-hydroxy-7-methylaminonaphthalene-3-sulphonic acid, and

1-hydroxy-6-aminonaphthalene-3,5-disulphonic acid.

Alternatively, the triazine group may be attached to the diazo componentof the dye. Suitable diazo components for this purpose include

1,3-diaminobenzene-4-sulphonic acid,

1,3-diaminobenzene-4,6-sulphonic acid,

1,4-diaminobenzene-3-sulphonic acid,

1,4-diaminobenzene-3,6-disulphonic acid,

3,7-diaminonapthalene-1,5-disulphonic acid,

N-methyl-p-phenylene diamine,

N-ethyl-m-phenylene diamine,

m-phenylene diamine and

4,4'-diaminostilbene-2,2'-disulphonic acid

which may be combined with coupling components such as

1-p-sulphophenyl-3-carboxypyrazol-5-one or

1-ethyl-2-hydroxy-3-carbonamido-4-methylpyrid-6-one.

Dyes of the invention may also be prepared by reacting a diamine offormula 9 with two moles of cyanuric chloride followed by the dyestuffcompound DNRH.

The reactions leading to the formation of the dyes of the invention maybe performed using conditions that have been fully described in theprior art for such reactions. Similarly, the dyes may be isolated byknown methods, for example spray drying or precipitation and filtration.As in the case of other dyes containing sulphonic acid groups, it isoften convenient to isolate and use the dyes in the form of theirwater-soluble salts, particularly their alkali metal (especially sodium)or ammonium salts. It is to be understood that the invention relates toboth the free acids and their salts.

The dyes of the present invention may be used for colouring a wide rangeof textile materials containing hydroxyl or amino groups, for examplewool, silk, synthetic polyamides and natural or regenerated cellulose,for example cotton or viscose rayon materials, by conventional methodsused for colouring such materials with water-soluble reactive dyes.Thus, in the case of cellulose they are preferably applied inconjunction with a treatment with an acid binding agent such as causticsoda, sodium carbonate, phosphate, silicate or bicarbonate, which may beapplied to the cellulose textile materials before, during or after theapplication of the dyestuff.

The dyes of the present invention are valuable reactive dyes forcellulose. They yield coloured textiles in various shades with goodresistance to washing and light. They are particularly characterised byhaving superior wash-off properties relative to the corresponding knowndyes containing a phenylene diamine residue instead of anaminobenzylamine residue.

The invention is further illustrated by the following examples in whichall parts and percentages are by weight unless otherwise indicated. Theexpression "M.I." indicates the weight in grams of dye or intermediatecontaining one gram-mole of pure product.

EXAMPLE 1

A solution of1-hydroxy-2-(2'-sulphophenylazo)-8-(4",6"-dichloro-s-triazin-2"-ylamino)-naphthalene-3,6-disulphonicacid (27.6 g, M.I. 1380, 0.02 mole) and N-methyl-m-aminobenzylamine(1.36 g, 0.1 mole) was stirred at 20° to 25° C. and pH 6 for 0.5 hoursfollowed by 3 hours at 30° to 35° C. and pH 8.5. On cooling, the pH wasadjusted to 7.0 with 2 N hydrochloric acid, a small amount of insolublematter was filtered off and salt (22% w/v) was added, with stirring. Theprecipitated product was collected, washed with brine (20%) and dried.Yield 18.0 g, M.I. 2000.

The product dyed cotton a bright yellowish red shade with good build upand wash off.

EXAMPLE 2

A solution of1-hydroxy-2-(2'-sulpho-4'-methylphenylazo)-6-(2",4"-dichloro-s-triazin-6"-ylamino)-naphthalene-3,5-disulphonicacid (12.8 g, M.I. 1021, 0.0125 mole) and N-methyl-m-aminobenzylamine(0.85 g, 0.00625 mole) was stirred at 20° C. and pH 6.5. After 30minutes, the pH was adjusted 8.5 and the temperature raised to 35° C.Further dichlorotriazinyl dye (0.7 g) was added to balance the reaction,the mixture was allowed to cool to 20° C., the pH was adjusted to 7.0and product was precipitated by the addition of sodium chloride (15%w/v) and potassium chloride (5% w/v). Yield 12.6 g, M.I. 2445.

The product dyed cotton a bright orange shade with good build up andwash off.

EXAMPLE 3

A solution of1-hydroxy-2-(1',5'-disulphonaphth-2'-ylazo)-6-(4",6"-dichloro-s-triazinylamino)-naphthalene-3,5-disulphonicacid (22.6 g, M.I. 1335, 0.0167 mole) and o-aminobenzylamine (1.016 g,0.0083 mole) was stirred at pH 8 and 35° C. for 2 hours. Furthero-aminobenzylamine (0.2 g) was added and heating continued for a further2 hours. On cooling to 20° C., salt (25% w/v) was added and the mixturewas stirred for 16 hours. precipitated solid was collected and dried.Yield 31.0 g, M.I. 3728.

The product was a bright orange which built up well and washed offeasily.

EXAMPLE 4

A solution of3-ureido-4-(3',6',8'-trisulphonaphth-2'-yl-azo)-N-(4",6"-dichloro-s-triazin-2"-yl)aniline(27.8 g, M.I. 1388, 0.02 m) and N-methyl-m-aminobenzylamine (1.36 g,0.01 m) was reacted as in Example 3. Further dichlorotriazine (0.5 g)was required to balance the reaction. After completion, the pH wasadjusted to 7.5, the solution was filtered to remove any insolublematerial and water was partially removed under reduced pressure to leavea solution, volume 150 ml. Ethanol (300 ml) was added slowly, withstirring, the precipitated product was washed and dried.

Yield 18.5 g, M.I. 2280.

The product dyed cotton a deep reddish yellowish shade with good washoff properties.

EXAMPLE 5

A solution of1-hydroxy-2-(1',5'-disulphonaphth-2'-ylazo)-6-(4",6"-dichloro-s-triazin-2"-ylamino)-naphthalene-3,5-disulphonicacid (135.25 g) and N-methyl-m-aminobenzylamine (5.66 g) was stirred atpH 8.5 to 9.0 and at 35° to 40° C. After 2.5 hours, had been consumedand further small portions were added up to a total of 0.81 g over 4.5hours after which the reaction appeared complete as judged by hplc. Themixture was allowed to cool to 20° C., the pH was adjusted to 7.0 with 2N hydrochloric acid, the solution was filtered to remove any traces ofinsoluble matter and salt (25% w/v) added with stirring. After 16 hoursthe precipitated orange product was collected and dried. Yield 113.49.

EXAMPLE 6

By the same general method1-hydroxy-2-(2'-sulpho-4'-methylphenylazo)-6-(4",6"-dichloro-s-triazin-2"-ylamino)-naphthalene-3,5-disulphonicacid was condensed with a half equivalent of m-aminobenzylamine to givean orange dye.

Other dyes prepared by a similar procedure are listed in Table 1, thechlorotriazine group being attached to the coupling component.

                  TABLE 1                                                         ______________________________________                                        Ex-                                                                           am-  Diazo      Coupling    Linking                                           ple  Component  Component   Diamine   Shade                                   ______________________________________                                         7   2-Amino-   1-Hydroxy-  o-Amino-  Bluish                                       naphthalene-                                                                             8-amino-    benzylamine                                                                             red                                          1,5-disulpho                                                                             naphthalene-                                                                  3,6-disulpho                                                   8   2-amino-   1-Hydroxy-  m-amino-  Bluish                                       naphthalene-                                                                             8-amino-    benzylamine                                                                             red                                          1-sulpho   naphthalene-                                                                  3,6-disulpho                                                   9   2-amino-   1-Hydroxy-  N-beta-   Bluish                                       naphthalene-                                                                             8-amino-    hydroxyethyl-                                                                           red                                          1,5-disulpho                                                                             naphthalene-                                                                              m-amino-                                                          3,6-disulpho                                                                              benzylamine                                       10   2-amino-   3-amino-4-  p-amino-  Red-                                         naphthalene-                                                                             methoxy-    benzylamine                                                                             dish                                         4,8-disulpho                                                                             acetanilide           yellow                                  11   Aniline-   1-Hydroxy-  m-amino-  Green-                                       2,5-disulpho                                                                             6-amino-    benzylamine                                                                             ish                                                     naphthalene-          orange                                                  3-sulpho                                                      12   2-amino-   2,6-xylidine                                                                              2,4-disulpho-                                                                           Yellow                                       naphthalene-           5-amino-N-                                             3,6,8-trisulpho        methylbenzyl-                                                                 amine                                             13   Aniline-2,5-                                                                             2,6-dimethoxy-                                                                            N-n-butyl-                                                                              Yellow                                       disulpho   aniline     3-amino-                                                                      benzylamine                                       14   2-sulpho-  2-methoxy-5-                                                                              4-amino-  Yellow                                       4-methyl-  methylaniline                                                                             benzylamine                                            aniline                                                                  15   Aniline-2,4-                                                                             1-(2'-methyl-                                                                             3-amino-  Green-                                       disulpho   3'-amino-5'-                                                                              N-methyl- ish                                                     sulphophenyl)-                                                                            benzylamine                                                                             yellow                                                  3-carboxy-                                                                    pyrid-5-one                                                   16   2-amino-   1-beta-amino-                                                                             3-amino-  Green-                                       naphthalene-                                                                             ethyl-2-    6-chloro- ish                                          1,5-disulpho                                                                             hydroxy-3-  N-methyl- yellow                                                  carbonamido-                                                                              benzylamine                                                       4-methyl-                                                                     pyrid-6-one                                                   17   2-amino-5- 1-hydroxy-7-                                                                              m-amino-  Yellow-                                      methoxyben-                                                                              methylamino-                                                                              benzylamine                                                                             ish                                          zene sulpho                                                                              naphthalene-          red                                                     3-sulpho                                                      18   2-amino-   1-hydroxy-7-                                                                              m-amino-  Orange                                       benzene-   amino       benzylamine                                            1,5-disulpho                                                                             naphthalene-                                                                  3-sulpho                                                      19   2-amino-   1-hydroxy-8-                                                                              m-amino-  Bluish-                                      naphthalene-                                                                             amino-      benzylamine                                                                             red                                          1-sulpho   naphthalene-                                                                  3,5-disulpho                                                  ______________________________________                                    

Dyes in which the reactive group is attached to the diazo component arelisted in Table 2.

                  TABLE 2                                                         ______________________________________                                        Ex-   Diazo      Coupling    Linking                                          ample Component  Component   Diamine  Shade                                   ______________________________________                                        20    2,4-diamino-                                                                             1-ethyl-2-  m-Amino- Greenish                                      benzene-1,5                                                                              hydroxy-3-  benzylamine                                                                            yellow                                        disulpho   carbonamido-                                                                  4-methyl-                                                                     pyrid-6-one                                                  21    2,4-diamino-                                                                             1-(4'-sulpho-                                                                             N-Ethyl- Greenish                                      benzene-1,5                                                                              phenyl)-3-  m-amino- yellow                                        disulpho   methylpyrazol-                                                                            benzylamine                                                       5-one                                                        22    2,5-diamino-                                                                             1-(4'-sulpho-                                                                             N-isopropyl-                                                                           Reddish                                       benzene-1,4-                                                                             phenyl)-3-  m-amino- yellow                                        disulpho   carboxy-    benzylamine                                                       pyrazolone                                                   23    2,5-diamino-                                                                             1-(4'-sulpho-                                                                             m-amino- Reddish                                       benzene-1,4-                                                                             phenyl)-3-  benzylamine                                                                            yellow                                        disulpho   carboxy-                                                                      pyrazolone                                                   24    2,4-diamino-                                                                             1-Ethyl-2-  m-amino- Greenish                                      benzene    hydroxy-3-  benzylamine                                                                            yellow                                        sulpho     cyano-4-                                                                      methyl                                                       25    2,4-diamino-                                                                             1-Hydroxy-6-                                                                              N-methyl-                                                                              Orange                                        benzene    acetylamino-                                                                              m-amino                                                           naphthalene-                                                                              benzylamine                                                       3-sulpho                                                     ______________________________________                                    

EXAMPLE 26

1.066 g of m-aminobenzylamine dissolved in acetone (20 ml) was added toa stirred solution of1-hydroxy-2-(1',5'-disulphonaphth)-2'-yl-azo)-6-(4",6"-dichloro-s-triazin-2"-ylamino)-naphthalene-3,5-disulphonicacid (22.57 g, M.I. 1355) in water (500 ml). The mixture was stirred atpH 6 to pH 7 at 20° C. for 30 minutes and then at pH 8.5 and 35° C. for4.5 hours. The mixture was screened and salt (15% w/v) added to thefiltrate. The resulting precipitated orange dye was collected, washedwith brine (20%) and dried.

Yield 13.1 g, M.I. 2480.

EXAMPLE 27

A solution of m-aminobenzylamine (0.59 g) in acetone (10 ml) was addedto a stirred solution of1-hydroxy-2-(1',5'-disulphonaphth)-2'-yl-azo)-8-(4",6"-dichloro-s-triazin-2"-ylamino)-naphthalene-3,6-disulphonicacid (21.89 g, M.I. 2188) in water (200 ml). The reaction mixture wasstirred at 20° C. and at pH 6 to 7 for 2 hours, then at 30° to 35° C.and pH 8.0 to 8.5 for 3 hours. After filtering to remove any traces ofinsoluble product, ethanol was added and the resulting precipitatedbluish-red dye collected and dried.

Yield 14.6 g, M.I. 2737.

When N-methyl-m-aminobenzylamine (0.68 g) was substituted form-aminobenzylamine in the above reaction and the desired productcollected as above, the yield of bluish-red product was 14.1 g M.I.2619.

EXAMPLE 28

A solution of N-methyl-m-aminobenzylamine (1.36 g) in acetone (20 ml)was added to a stirred solution of1-hydroxy-2-(1'-sulphonaphth)-2'-ylazo)-8-(4",6"-dichloro-s-triazin-2"-ylamino)-naphthalene-3,6-disulphonicacid (21.28 g, M.I. 1064). After stirring at pH 6 and 20° C. for 1 hour,the temperature was maintained at 35° C. for 28 hours. Any insolublematerial was filtered off, the filtrate concentrated to 100 ml and thebluish-red dye precipitated by adding ethanol with stirring.

Yield 20.4 g, M.I. 2065.

EXAMPLE 29

A solution of m-aminobenzylamine (1.525 g) in acetone (20 ml) was addedto a stirred solution of3-acetylamino-4-(3',6',8'-trisulphonaphth)-2'-ylazo)-N-(4",6"-dichloro-s-triazin-2"-yl)-aniline(28.62 g, M.I. 1145) at pH 6.5 and 20° C. After 30 minutes, the pH wasraised to 8.5 and the temperature to 35° C. After a further 5 hours, thereaction was essentially complete, as judged by h.p.l.c., and wasscreened. Ethanol (170 ml) was added to the stirred filtrate (500 ml)and the resulting precipitated golden-yellow dye collected.

Yield 17.0 g, M.I. 2572.

EXAMPLE 30

A solution of N-methyl-m-aminobenzylamine (1.36 g) in acetone (20 ml)was added to a stirred solution of3-acetylamino-4-(3',6',8'-trisulphonaphth)-2'-ylazo)-N-(4",6"-dichloro-s-triazin-2"-yl)-aniline(22.9 g, M.I. 1145). The mixture was stirred for 1 hour at pH 6.5 at 25°C., then 1 hour at pH 8.5. The yellow product was precipitated withethanol.

Yield 16.8 g, M.I. 2438.

Further dyes of Formula 1, made by the interaction of a dyestuffcompound of formula DNRH, cyanuric chloride and a diamine of Formula 3,are shown in the following Table 3.

                  TABLE 3                                                         ______________________________________                                        DNRH               Linking Diamine                                                                            Shade                                         ______________________________________                                        1-Amino-4-(3'-amino-4'-sulpho-                                                                   m-amino      Bright                                        anilino)anthraquinone-                                                                           benzylamine  blue                                          2-sulphonic acid                                                              Copper complex of 8-amino-                                                                       N-isopropyl- Violet                                        1-hydroxy-2-(2'-hydroxy-                                                                         m-amino                                                    5'-sulphophenylazo)naphthalene-                                                                  benzylamine                                                3,6-disulphonic acid                                                          The 1:2-chromium complex of                                                                      m-amino      Black                                         8-amino-1-hydroxy-2-(4'-nitro-                                                                   benzylamine                                                2'-hydroxyphenylazo)naphthalene-                                              3,6-disulphonic acid                                                          Copper complex of N-(2-hydroxy-                                                                  m-amino      Blue                                          5-sulpho-3-aminophenyl)-N'-                                                                      benzylamine                                                (2'-carboxy-4'-sulphophenyl)-                                                 ms-formazan                                                                   Copper complex of N-(2-hydroxy-                                                                  N-hydroxyethyl-                                                                            Blue                                          4-sulpho-3-aminophenyl)-N'-                                                                      m-amino                                                    (2'-carboxy-4'-sulphophenyl)-                                                                    benzylamine                                                ms-formazan                                                                   Copper complex of N-(2-hydroxy-                                                                  N-methyl-    Blue                                          5-amino-3-sulphophenyl)-N'-                                                                      m-amino                                                    (2'-carboxy-4'-sulphophenyl)-                                                                    benzylamine                                                ms-formazan                                                                   ______________________________________                                    

I claim:
 1. A water-soluble reactive dye of the formula: ##STR13##wherein D represents a chromophore selected from the group consisting ofazo, anthraquinone and triphenodioxazine, each of which has one orrepresents hydrogen or an C₁₋₈ -alkyl which is unsubstituted orsubstituted by a substituent selected from the group consisting halogen,hydroxy, cyano, carboxy, carbamoyl, or phenyl and Q represents a groupof the formula: ##STR14## wherein each of X and Y, independently,represents halogen, ntiro, carboxy or sulpho and each of n and m,independently, represents an integer from 0 to
 2. 2. A reactive dyeaccording to claim 1 wherein D is a sulphonated monoazo group.
 3. Areactive dye according to claim 2 wherein D is a group of the formula:##STR15## wherein A is a sulphonated phenyl or naphthyl group and one ofU and V is SO₃ H and the other is H.
 4. A reactive dye according toclaim 2 wherein D is a group of the formula: ##STR16## wherein A is asulphonated phenyl or naphthyl group.
 5. A reactive dye according toclaim 3 wherein A is a sulphonated phenyl or sulphonated naphthyl group.6. A reactive dye according to claim 5 wherein the sulpho group in A isin an ortho position relative to the azo link.
 7. A reactive dyeaccording to claim 6 wherein A is a group of the formula: ##STR17##wherein Z¹ represents H, SO₃ H, C₁₋₄ -alkyl or C₁₋₄ -alkoxy.
 8. Areactive dye according to claim 6 wherein A is a group of the formula:##STR18## wherein Z² represents H or SO₃ H.
 9. A reactive dye accordingto claim 2 wherein D is a group of the formula: ##STR19## wherein A is asulphonated naphthyl group, M¹ is hydrogen or C₁₋₄ -alkoxy and T is C₁₋₄-alkyl or --NH₂.
 10. A water-soluble reactive dye which, in the freeacid form, is of the formula: ##STR20## wherein each of R, R¹ and R²independently is H or C₁₋₄ -alkyl; each X and Y independently ishalogen, nitro, carboxy or sulpho;each of n and m independentlyrepresents an integer from 0 to 2; D is selected from the groupconsisting of: ##STR21## wherein one of U and V is SO₃ H and the otheris H; and A is a sulphonated naphthyl group; M¹ is H, C₁₋₄ -alkyl orC₁₋₄ -alkoxy; M² is H, C₁₋₄ -alkyl or C₁₋₄ -alkoxy or --NHCOT where T isC₁₋₄ -alkyl or --NH₂.
 11. A water-soluble reactive dye which, in thefree acid form, is of the formula: ##STR22## wherein each of R, R¹ andR² independently is H or C₁₋₄ -alkyl; each X and Y independently ishalogen, nitro, carboxy or sulpho;each of n and m independentlyrepresents an integer from 0 to 2; D is selected from the groupconsisting of: ##STR23## wherein A is 1,5-disulphonaphth-2-yl.
 12. Awater-soluble reactive dye which, in the free acid form, is of theformula: ##STR24## wherein each of R, R¹ and R² independently is H orC₁₋₄ -alkyl; each X and Y independently is halogen, nitro, carboxy orsulpho;each of n and m independently represents an integer from 0 to 2;D is ##STR25## wherein M¹ is H, C₁₋₄ -alkyl or C₁₋₄ -alkoxy; M² is H,C₁₋₄ -alkyl or C₁₋₄ -alkoxy or --NHCOT; T is C₁₋₄ -alkyl or --NH₂ ; A is3,6,8-trisulphonaphth-2-yl, 1,5-disulphonaphth-2-yl or1,5,7-trisulphonaphth-2-yl.
 13. A water-soluble reactive dye of theformula: ##STR26## wherein D is a sulphonated azonaphthalene orsulphonated phenylazonaphthalene radical, R is H or C₁₋₄ -alkyl, each ofR¹ and R², independently, is H, C₁₋₄ -alkyl or hydroxy-C₁₋₄ -alkyl, eachof X and Y, independently, is halogen, sulpho and each of n and m,independently, represents an integer from 0 to
 2. 14. A reactive dyeaccording to claim 13, wherein D, in the free acid form, is selectedfrom the group consisting of ##STR27## wherein A is a sulphonated phenylor sulphonated naphthyl radical and one of U and V is SO₃ H and theother is H.
 15. A reactive dye according to claim 14, wherein A isselected from the group consisting of ##STR28## wherein Z¹ is H, SO₃ H,C₁₋₄ -alkyl or C₁₋₄ -alkoxy and Z² is H or SO₃ H.